Plasma fluorine resistant alumina ceramic material and method of making

ABSTRACT

A plasma fluorine resistant polycrystalline alumina ceramic material is produced by forming a green body including alumina and a binder, and sintering the green body for a time from about 8 to 12 hours. The area % of unsintered particles in the polycrystalline alumina ceramic material does not exceed 0.1 area %, resulting in reduced emission of particles from the material after exposure to plasma fluorine.

This application is a divisional application of application Ser. No.08/424,772, filed Apr. 18, 1995, now U.S. Pat. No. 6,083,451 which iscurrerntly pending.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an improved alumina ceramic materialwhich is highly resistant to etching by fluorine plasmas and ischaracterized by reduced particle emission. The present inventionfurther relates to a method for making the improved ceramic material,and to articles of manufacture comprising the improved ceramic material.

2. Description of the Related Art

Polycrystalline alumina ceramic materials typically are produced by thefollowing sintering process. Powdered alumina, having a desired spectrumof grain sizes (typically having an average size of about 1 μm to 3 μm)is combined with a binder, and the combined alumina powder and binderare then compacted to form a green body. Commonly the green body has acomposition including about 99.5 wt % alumina and about 0.5 wt % of amixture of silica, MgO and CaO as a binder. The green body issubsequently sintered, typically in air under ambient pressure(“pressureless sintering”) and at a temperature of about 1650° C., for atime of about 4 hours.

During the sintering process, grain growth occurs. For example, commonsintering processes yield a distribution of sintered grain sizes rangingfrom about 1 to about 30 μm with a mean grain size of about 6 μm, asdetermined by well known methods such as those set forth in AmericanSociety for Testing and Materials (ASTM) standards E 1181-87(determination of duplex grain sizes) and E 112-88 (determination ofaverage grain sizes (AGS)). Growth of the alumina grains causesdisplacement of the binder phase. The displaced binder phase migrates toareas in which smaller grains are present and surround the smallergrains. Since alumina is very immiscible in silica, the primarycomponent of the typical binder phase (see J. W. Welch, Nature, vol.186, p. 546 et seq. (1960)), the surrounding binder phase preventsfurther growth of the isolated smaller grains. These isolated unsinteredgrains can range from about 0.1 to 0.5 μm in diameter. Typically, about1% of the alumina grains remain unsintered.

While known polycrystalline alumina ceramic materials have desirableproperties, such as high strength and fracture toughness, they haveproven insufficiently resistant to certain fluorine plasmas forapplications in which exposure to such plasmas is required. Knownaluminas are particularly susceptible to etching by fluorine plasmas,such as those generated in chemical vapor deposition (CVD) reactorsduring chamber cleaning processes. In such processes, plasma fluorineliberated from fluorocarbon and other fluorine-containing gases (forexample, NF₃ plasmas, CF₄:O₂ plasmas and CF₄:N₂O plasmas) are used toremove dielectric film residues deposited in the chambers of thereactors.

Alumina per se is highly resistant to plasma fluorine; thus, sapphire,which is pure single-crystal alumina, is one of the slowest etchingmaterials known.

Etching of polycrystalline alumina ceramic materials occurs primarily inthe binder phase. As a result of etching of the binder phase, the smallunsintered particles can be dislodged. The dislodged particles can thenbe emitted from the surface of the ceramic materials. Suchpolycrystalline alumina ceramic materials constitute a source ofcontamination when used in CVD reactors and other environments exposedto plasma fluorine.

Solutions to the particle emission problem which have been consideredinclude the production of a polycrystalline alumina ceramic having anincreased proportion of alumina, e.g., 99.9 wt % alumina and 0.1 wt %binder; use of a different binder which is less sensitive to fluorineplasma; use of a ceramic material other than alumina; and modificationof the initial distribution of alumina grain sizes in the green body.

A particular application in which particle emission is problematic is inthe processing of semiconductor wafers in chemical vapor deposition(CVD) systems, for example, in the “5000” apparatus provided by AppliedMaterials, Inc. as described by Chang et al. in U.S. application Ser.No. 08/136,529. An exemplary prior art CVD reactor is illustrated inFIGS. 1 and 2. In FIG. 1, a CVD system 10 comprises deposition chamber12, vacuum channel 13, vacuum exhaust system 14, gas inlet means 16, gasdistribution shield 17, blocker 18, wafer lift 20, baffle plate 22, liftfingers 24 and susceptor lift 26. A substrate 28, such as asemiconductor wafer, is disposed on a susceptor 30. Heating means 32,for example an external array of 1000 watt lamps directing collimatedlight through quartz window 36, maintains a uniform processingtemperature. The deposition or reaction zone 34 lies above thesubstrate.

Gas distribution shield 17 is a flat annular element which surroundsblocker 18 and is removably affixed to chamber lid 38 by a plurality ofaluminum clips 40, as shown in FIG. 2. Gas distribution shield 17 istypically comprises of a polycrystalline alumina ceramic material.

In a typical deposition process carried out in the illustrated CVDsystem, process gases (i.e., reaction and carrier gases) enter into thedeposition chamber 12 via gas inlet means 16 and “showerhead” typeblocker 18. The blocker 18 has numerous openings over an areacorresponding to that of the substrate 28 beneath it. The spacingbetween the.blocker 18 and the substrate 28 can be adjusted to fromabout 200-1000 mils (5-25 mm) to define the reaction zone 34. Theblocker 18 feeds the combined process gases to the reaction zone 34. Thedeposition reaction is carried out, and the gases are purged fromchamber 12. After each wafer is processed, the chamber is cleaned usinga cleaning gas such as NF₃ or a C₂F₆/NF₃/O₂ gas mixture.

When gas distribution shield 17 is comprised of a polycrystallinealumina ceramic material, however, the shield is subject to etching bythe cleaning gas or gas mixture as described above, with resultantparticle emission. Particles having sizes from about 0.2 to 0.5 μm canbe emitted and can contaminate silicon wafers processed in the CVDapparatus. Particle counts of up to 200/cm² or higher can be observed onthe surfaces of the silicon wafers after 100 wafers have been processed.Such particle counts are unacceptably high.

A continuing need exists for improved polycrystalline alumina ceramicmaterials and methods for producing them. The materials should show highresistance to plasma fluorine, and in particular show reduced particleemission. A specific need exists for gas distribution shields, for usein a CVD apparatus, which are comprised of such an improved material.

SUMMARY OF THE PREFERRED EMBODIMENTS

In accordance with one aspect of the present invention, there isprovided a method of producing a plasma fluorine resistantpolycrystalline alumina ceramic material which includes the steps offorming a green body comprising alumina and a binder, and sintering thegreen body for a time from about 8 to 12 hours.

In accordance with another aspect of the present invention, there isprovided a method of producing a plasma fluorine resistantpolycrystalline alumina ceramic material which includes the steps offorming a green body comprising alumina and a binder, and sintering thegreen body for a time such that the area % of unsintered particles inthe resulting alumina ceramic material does not exceed 0.1 area %.

In accordance with further aspects of the present invention, there areprovided a ceramic material produced according to a method as describedabove, and an article of manufacture comprising a ceramic material asdescribed above. Preferred embodiments of the inventive articles ofmanufacture include components useful in vacuum processing devices suchas CVD chambers, in particular gas distribution shields.

Other objects, features and advantages of the present invention willbecome apparent to those skilled in the art from the following detaileddescription. It is to be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the present invention, are given by way of illustrationand not limitation. Many changes and modifications within the scope ofthe present invention may be made without departing from the spiritthereof, and the invention includes all such modifications.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention may be more readily understood by referring to theaccompanying drawings in which

FIG. 1 is a schematic cross-sectional view of a prior art CVD apparatuswhich employs a gas distribution shield that can be comprised of apolycrystalline alumina ceramic material;

FIG. 2 is a perspective view of the CVD apparatus of FIG. 1 with openedchamber lid, showing the relationship of the gas distribution shield,blocker and chamber lid;

FIG. 3 is a photomicrograph (magnification×9,000) of a polycrystallinealumina ceramic material after a firing time of 4 hours, and

FIG. 4 is a photomicrograph (magnification×9,000) of a polycrystallinealumina ceramic material having the same composition as the material ofFIG. 3, after a firing time of 8 hours, illustrating the reduction inthe number of unsintered grains achieved according to the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

We have discovered that an alumina ceramic material which is highlyresistant to fluorine plasmas can be produced by lengthening the time offiring an alumina green body from the conventional time of about 4 hoursto about 8 to 12 hours, without the need for altering the composition ofthe green body or any other sintering process parameters, such as thesintering temperature, which may affect the sintering mechanism.

The increased sintering time for given sintering temperatures and greenbody compositions results in a reduction in the percentage of unsinteredgrains of up to an order of magnitude, i.e., to about 0.1 area % orless, as opposed to about 1 area % for the previously known aluminaceramic materials. The amount of particle emission from the ceramicmaterial upon exposure to plasma fluorine is correspondingly reduced.

A green body which is to be sintered to produce a polycrystallinealumina ceramic material according to the invention can be formed froman alumina powder having any desired composition. Preferred powdercompositions include about 99.3 wt % to 99.7 wt % of alumina, and about0.7 wt % to 0.3 wt % of a binder selected from the group consisting ofsilica, calcium oxide, magnesium oxide and mixtures thereof. The powdercomposition can have any conventional distribution of grain sizes.

The selected alumina powder is formed into the green body by means wellknown to those skilled in the art. The pressure employed to produce thegreen body preferably ranges from about 5,000 to 14,000 psia, morepreferably about 7,000 to 10,000 psia. Initial green body densitypreferably ranges from about 1.8 to 2.2 g/cm³.

The green body is subsequently sintered for a time from about 8 to 12hours. Sintering times longer than about 12 hours may result in theformation of second phase crystalline nucleations, thus undesirablyaltering the structure of the sintered body. Sintering times shorterthan about 8 hours do not achieve the desired reduction in the number ofunsintered grains and corresponding reduction in particle emission.Sintering times from about 8 to 10 hours are preferred for purposes ofprocess economy.

Preferably, the sintering process is a pressureless sintering processcarried out in air. The sintering process can also be carried out inother conventional sintering environments, such as inert gasatmospheres. The sintering process preferably is carried out at atemperature from about 1400° C. to 1700° C., more preferably about 1600°C. to 1650° C. It is emphasized that the invention affords an improvedsintering process in which only the length of the sintering time need bechanged. All other parameters of the sintering process can remainunchanged.

The plasma fluorine resistant alumina ceramic material producedaccording to the inventive process shows a significant reduction in thequantity of unsintered grains, as is evident from a comparison of thematerials illustrated in FIGS. 3 and 4.

As shown in FIG. 3, after a 4 hour soak, there are many particles havinga particle size considerably less than 3 μm. As shown in FIG. 4, afteran 8 hour soak, the particles typically have sizes ranging from about 3μm to about 10 μm.

The quantity of unsintered grains can be determined according to methodsknown to those skilled in the art. In one typical method, a plurality ofphotomicrographs (e.g., at 10×) of randomly selected regions of thealumina ceramic material are examined, and the presence of unsinteredparticles are determined by inspection. The areas of the unsinteredparticles are determined, and the total of the unsintered particle areasis divided by the total area of all of the photomicrographed regions ofthe alumina ceramic material. The quotient is the area %, and provides ameasure of the quantity of unsintered grains.

The alumina ceramic materials produced according to the process of theinvention show unsintered grain percentages of about 0.1 area % or less,preferably about 0.01 area % to 0.1 area %.

The particle emission from the alumina ceramic materials of theinvention upon exposure to plasma fluorine is correspondingly reduced.Particle contamination of a silicon wafer, for example, due todislodgment of particles from components of a CVD apparatus comprisingthe alumina ceramic material after exposure of the material to afluorine plasma can be quantified using standard techniques. Morespecifically, particle emission from the alumina ceramic material can bedetermined by measuring particle counts on the surface of the waferduring a deposition step carried out after CVD chamber cleaning.

According to a typical standard technique, the particle count isdetermined using a Tencor Surfscan 6200 wafer surface scanner,commercially available from Tencor Instruments Inc. of Mountain View,Calif. The Tencor Surfscan 6200 determines the number of particles on asurface by measuring the amount of light (provided by a 30 mW Ar-ionlaser having a wavelength of 488 nm) which is scattered by theparticles. The principles of operation of the Tencor Surfscan 6200 andrelated devices are discussed in Surface Contamination Detection: AnIntroduction (R. Johnson, Ed., Tencor Instruments Inc, Mountain View,Calif. 1990). Other known methods for determining the number ofparticles on the surface of a material can also be used.

Particle emission from alumina ceramic materials produced in accordancewith the inventive process is significantly reduced in comparison toalumina ceramic materials produced according to the correspondingconventional processes, i.e., processes in which sintering times areabout 1-4 hours but in which the remaining process parameters and greenbody compositions are the same. Typically the reduction in particleemission is at least about 50%, preferably at least about 60%, verypreferably about 60% to 90%, in comparison to correspondingconventionally produced ceramic materials, as determined by thepreferred procedure discussed above.

The inventive process affords a plasma fluorine resistant aluminaceramic material which can be employed in forming a variety of articlesof manufacture, preferably for use in environments wherein they aresubject to plasma fluorine exposure. Such articles of manufactureinclude, for example, bell jars, crucibles, and components for use witha vacuum processing apparatus. More specific articles of manufacturewithin the scope of the instant invention include vacuum processingapparatus components such as a gas distribution shield, a chuck, anozzle, a susceptor, a heater plate, a clamping ring, a wafer boat, or achamber wall. Such articles of manufacture can be comprised entirely orsubstantially of a ceramic material of the invention, or can have one ormore surfaces having coatings which comprise a ceramic material of theinvention.

Gas distribution shields particularly advantageously include theinventive alumina ceramic material as discussed herein. Such gasdistribution shields can be employed in a variety of known devices forprocessing silicon wafers, as well as other semiconductor materials.Particular known devices in which the foregoing gas distribution shieldscan be used with advantage include CVD devices provided by AppliedMaterials, Inc. of Santa Clara, Calif., such as those described by Changet al. in U.S. application Ser. No. 08/136,529, and by Tseng et al. inU.S. application Ser. No. 08/314,161, the disclosures of each of whichare incorporated herein in their entireties by reference. More specificexamples include the Precision 5000 CVD reactor (commercially availablefrom Applied Materials, Inc.) The instant invention is furtherillustrated by reference to the following non-limiting examples.

EXAMPLE 1

An alumina powder (commercially available from Alcoa) was combined withpowdered silica, MgO and CaO to afford a composition comprising 99.5 wt% alumina, 0.2 wt % silica, 0.15 wt % MgO and 0.15 wt % CaO. Thecomposition was ball milled to produce a mean particle size of 0.2 μm.The composition was then compressed to produce green bodies in the formof gas distribution shields having diameters of about 13 inches, with abore diameter of about 6 inches, thicknesses of 0.25 inch, and densitiesof 3 g/cm³.

Pressureless sintering of the green bodies according to the inventionwas carried out in air at 1650° C. for 8 hours nominal sintering time (8hours actual maintenance at 1650° C.).

The particle emission of each sintered gas distribution shield was thenmeasured. Each shield was installed in a Precision 5000 CVD reactor, and150 mm (6″) diameter silicon wafers were processed in the reactor inwhich the shield was installed.

Conventional Si₃N₄ chemical vapor deposition processes, with chambercleaning, were carried out in the CVD reactor as follows. A siliconwafer was introduced into the vacuum deposition chamber of the CVDreactor and heated to 400° C. SiH₄ (180 sccm), N₂ (1800 sccm) and NH₃(75 sccm) were introduced into the chamber, and the chamber pressure wasstabilized to 4.5 Torr. A 450 watt plasma was then ignited in thechamber, and deposition was carried out for 1 minute. The chamber wassubsequently pumped down to base pressure (100 mTorr), and the wafer wasremoved.

After the wafer was removed, the chamber was cleaned using a plasmacleaning process. CF₄ (1500 sccm) and N₂O (750 sccm) were introducedinto the chamber, pressure was stabilized to 5 Torr, and a 750 wattplasma was ignited in the chamber. Plasma cleaning was carried out for30 seconds. The chamber was subsequently pumped down to base pressure.

Next, the chamber was seasoned by deposition of Si₃N₄ in the chamber for15 seconds. The seasoning step was carried out in the same manner as thedeposition step described above.

In a first testing procedure, the seasoning step was carried after everycleaning cycle. In a second testing procedure, the seasoning step wasomitted. Prior to and subsequent to CVD deposition, the number ofparticles having sizes greater than 0.2 μm on the surfaces of thesilicon wafers were counted using a Tencor Surfscan 6200 wafer surfacescanner in the manner described herein, and the differences werecalculated.

The following results were observed:

Particle count on Si wafer 8 hour sintered shield with seasoning withoutseasoning after 5 wafers 25-30 25-30 after 200 wafers 25-30 25-30

EXAMPLE 2 Comparison With Known Process

Green bodies were formed from ball-milled alumina as described above,but were sintered according to a known process in which the nominalsintering time was 4 hours (4 hours actual maintenance at 1650° C.) toform comparison gas distribution shields. All other process conditionswere identical to those used in Example 1.

The particle emission of each comparison shield was then measured inexactly the same manner as described in Example 1. The following resultswere observed:

Particle count on Si wafer 4 hour sintered shield with seasoning withoutseasoning after 5 wafers 7 35 after 200 wafers 35 400

Comparison with the results from Example 1 reveals that the shieldsproduced according to the inventive method are characterized bysignificant improvements in particle emission upon exposure to plasmafluorine. Particle emissions from the inventive shields are both low innumber and substantially constant over many wafer processing cycles.

The reduction in particle emission achieved according to the inventionis particularly significant in comparison to the known method which doesnot include a seasoning step. Particle emission from the comparisonshields after 200 wafer processing cycles was up to 800% greater thanthat observed from the inventive shields after the same number of waferprocessing cycles.

The inventive material overcomes the difficulties associated with priorart alumina ceramic materials with respect to grain pull-out, is simpleto manufacture and provides a medium for inexpensive mass production ofvacuum deposition apparatus components, such as gas distributionshields, and other articles of manufacture.

Vacuum deposition apparatus, in particular CVD reactors, which employcomponents comprising the inventive alumina ceramic material are capableof processing silicon wafers and other materials that show reducedparticulate contamination.

What is claimed is:
 1. A plasma fluorine resistant polycrystallinealumina ceramic body having less than 0.1 surface area % of unsinteredparticles and having a mean sintered particle size ranging from about 3μm to about 10 μm produced by the following method: (i) forming a greenbody comprising alumina and a binder; and (ii) sintering said green bodyat a temperature ranging from about 1400° C. to about 1700° C. for atime period ranging from about 8 hours to about 12 hours.
 2. The plasmafluorine resistant polycrystalline alumina ceramic body of claim 1,wherein the surface area % of unsintered particles in saidpolycrystalline alumina ceramic body ranges from about 0.01 surface area% to about 0.1 surface area %.
 3. A plasma fluorine resistantpolycrystalline alumina ceramic body having less than 0.1 surface area %of unsintered particles and having a mean sintered particle size rangingfrom about 3 μm to about 10 μm produced by the following method: (i)forming a green body comprising about 99.3 wt % to about 99.7 wt % ofalumina and about 0.7 wt % to about 0.3 wt % of a binder selected fromthe group consisting of silica, calcium oxide, magnesium oxide andmixtures thereof; and (ii) sintering said green body at a temperatureranging from about 1400° C. to about 1700° C. for a time period rangingfrom about 8 hours to about 12 hours.
 4. A plasma fluorine resistantpolycrystalline alumina ceramic body comprising about 99.3 wt % to about99.7 wt % of alumina and about 0.7 wt % to about 0.3 wt % of a binderselected from the group consisting of silica, calcium oxide, magnesiumoxide and mixtures thereof, wherein said polycrystalline ceramic bodyhas a mean sintered particle size ranging from about 3 μm to about 10 μm. and wherein the surface area % of unsintered particles in saidpolycrystalline alumina ceramic body does not exceed 0.1 surface area %.5. A plasma fluorine resistant polycrystalline alumina ceramic bodyhaving less than 0.1 surface area % of unsintered particles and having amean sintered particle size ranging from about 3 μm to about 10 μmproduced by the following method: (i) providing a starting compositioncomprising alumina and a binder; (ii) comminuting said startingcomposition to produce an intermediate composition having a meanparticle size of about 0.2 μm; (iii) forming a green body comprisingsaid intermediate composition; and (iv) sintering said green body at atemperature ranging from about 1400° C. to about 1700° C. for a timeperiod ranging from about 8 hours to about 12 hours.
 6. The plasmafluorine resistant polycrystalline alumina ceramic body of claim 5,wherein said starting composition comprises about 99.3 wt % to about99.7 wt % of alumina and about 0.7 wt % to about 0.3 wt % of a binderselected from the group consisting of silica, calcium oxide, magnesiumoxide and mixtures thereof.